CN110057476A - A kind of multi signal response flexible electronic skin and preparation method thereof - Google Patents
A kind of multi signal response flexible electronic skin and preparation method thereof Download PDFInfo
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- CN110057476A CN110057476A CN201910453279.1A CN201910453279A CN110057476A CN 110057476 A CN110057476 A CN 110057476A CN 201910453279 A CN201910453279 A CN 201910453279A CN 110057476 A CN110057476 A CN 110057476A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/18—Measuring force or stress, in general using properties of piezo-resistive materials, i.e. materials of which the ohmic resistance varies according to changes in magnitude or direction of force applied to the material
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Abstract
The invention discloses a kind of multi signal response flexible electronic skins and preparation method thereof.The flexible electronic skin is interconnected to form by conductive micro-balloons, is PDMS microballoon inside conductive micro-balloons, and PDMS microsphere surface covers conductive layer and forms shell structurre, and the partial size of the PDMS microballoon is 6-40 microns, and the shell thickness is 20 nanometers -30 microns.The preparation method comprises the following steps: emulsifier is added and forms lotion, PDMS microballoon is obtained after solidification after PDMS, curing agent, water are mixed；It is mixed again with PDMS microballoon after PDMS, curing agent, conductive powder body are mixed, stirs evenly, form the raw material ink of 3D printing；Flexible electronic skin is made by 3D printer printing-forming in raw material ink.Conductive layer in the present invention is that PDMS is collectively constituted with conductive powder body, so that conductive layer is more stable, secured in conjunction with PDMS microballoon；Electronic skin obtained has sensitive mechanical response ability, electric performance stablity.
Description
Technical field
The invention belongs to flexible sensing technical fields, and in particular to a kind of multi signal response flexible electronic skin and its preparation
Method.
Background technique
With the development of society, flexible wearable device has incorporated the every aspect of human lives.In recent years, flexible electrical
The development of sub- strain sensing devices is very fast, can be used to detect various human physiological activities, including hand, arm by a relatively large margin
The bending of arm and leg is mobile and breathing more by a small margin, swallow, sounding when muscle vibration, blood pressure and intraocular pressure etc..Wearable electricity
Physiological activity signal is converted to visual electric signal by sub- sensor in the form of signal transduction, in human clinical's diagnosis, health
The fields such as assessment, health monitoring, virtual electronic, flexible touch screen, flexible electronic skin, or even industrial robot possess very big
Application potential.
It is sensed in numerous applications in flexible electronic, studying most commonly used is electronic skin.However the skin of the mankind is one
A very sensitive organ, it has integrated, telescopic network sensing function, can be by extraneous temperature, humidity and touching
The stimulus signals such as feel, which are transmitted to brain and receive the instruction that brain is sent, makes feedback, enables us to the ring that averts danger or experience
Border variation.People expect flexible electronic sensing technology being used for wearable electronic skin, and it is expected that it can be as the skin of people
Equally experience the sophisticated signals such as extraneous temperature, pressure, deformation or texture, and is converted environmental stimuli to by electronic skin
The electric signal that can be transmitted exports or even conveys the order of brain.Plum great waves of Hefei Institute Of Intelligent Machines Chinese Academy Of Sciences et al. application
Patent " flexible 3 D force-touch sensor ", publication number CN1796954A, structure includes flexible 3 D force-touch sensor,
By play a supportive role elastic substrates, three-dimensional force sensitization array and flexible packing material, flexible circuit board and shield
Elastic protective layer's composition, becomes a hard-packed three-dimensional force sensing element.The touch sensor processing technology is complicated, lacks
Highly flexible is not able to satisfy the demand of the man-machine integration in wearable device, does not mention with the differences of mechanical properties of human skin
And.Patent " touch sensor based on flexible pressure-sensitive conductive rubber " publication number of yellow English of HeFei University of Technology et al. application
CN101231200A, structure use flexible circuit board for bottom plate, and the flexible pressure-sensitive conductive rubber of disc-shaped is placed in flexible circuit
It on plate, and is electrically connected with the electrode being distributed on flexible circuit board, power transmission half is covered on the top stress surface of flexible pressure-sensitive conductive rubber
Ball, which has highly flexible on the whole, however pressure-sensitive conductive rubber has high lagging characteristics, poor linearity, precision
It is to be improved with resolution ratio.Patent " wearable pressure sensor and its manufacturer of Gaoyang of East China University of Science et al. application
Method " publication number CN108318161A, structure use flexible PDMS film for bottom plate, and PDMS microballoon is coated on PDMS film,
Then carbon nano-tube aqueous solutions are coated on surface, form conductive layer after dry, two parts conductive film stacked relative is taken to prepare
At pressure sensor, however the touch sensor is coated on the conductive layer of PDMS microsphere surface formation by carbon nano-tube aqueous solutions
Binding force is not strong between microballoon, is not difficult to help bread to PDMS microspheroidal simultaneously and cover, and device sensitivity is to be improved, and with
The differences of mechanical properties of human skin does not refer to.Currently, the research center of gravity of many researchers is mainly in electronic skin to pressure
In signal response, and it is relatively fewer to the response investigations of shearing force, and Chunhong Mu etc., which has studied, utilizes carbon nanotube and oxidation
The compound dimethyl silicone polymer of graphene has synthesized porous dimethyl silicone polymer (PDMS) film using pore-foaming agent, not only may be used
To detect the movement of wrist, different surface roughnesses can also be distinguished.Although electronic skin research in recent years achieves considerable
Progress, but still there are the response sensitivities of inductive material insufficient, stability and anti-interference ability is poor and the narrow range of induction
Etc. problems, these limit its practical application.
Summary of the invention
It is an object of the present invention to provide a kind of, and the multi signal with accurate response pressure, shearing force responds flexible electronic skin
Skin and preparation method thereof.
Present invention technical solution used for the above purpose is as follows:
A kind of multi signal response flexible electronic skin, the flexible electronic skin inside is PDMS microballoon, PDMS microballoon table
Face covers conductive layer and forms shell structurre, and the partial size of the PDMS microballoon is 6-40 microns, and the shell thickness is 20 nanometer -30
Micron.Heretofore described PDMS refers both to dimethyl silicone polymer.
Preferably, the conductive layer is the mixture of PDMS and conductive powder body, and the additive amount of the conductive powder body is skin
The 1.8%-2.4% of gross mass.
Preferably, the conductive powder body is in carbon nanotube, graphene, graphene oxide, modified graphene oxide
It is one or more.
The present invention also provides the preparation methods of multi signal response flexible electronic skin, and the method includes as follows
Step:
Step 1, it prepares PDMS microballoon: PDMS, curing agent, water being mixed according to a certain percentage, emulsifier is then added, mix
Conjunction is formed uniformly lotion, and solidification, deionized water is rinsed, and centrifugation obtains PDMS microballoon；
Step 2, the PDMS microballoon ink of conductive layer cladding is prepared: according to a certain percentage by PDMS, curing agent, conductive powder body
Mixing, mixture stir evenly after mixing according to a certain percentage with the PDMS microballoon of aforementioned preparation, form the raw material ink of 3D printing
Water；
Step 3, by the raw material ink of preparation by 3D printer printing-forming, flexible electronic skin is made in solidification.
Preferably, PDMS in the step 1, curing agent, water mass ratio be (8-12): 1:50.Further preferably
10:1:50.
Preferably, the additional amount of emulsifier is 4-8wt%, further preferably 6wt% in the step 1.
Preferably, the emulsifier in the step 1 is carboxyl chitosan.
Preferably, solidification temperature is 70-90 DEG C in the step 1, and curing time is 1-3 hours；Solidification temperature is further
Preferably 80 DEG C, curing time is 2 hours.
Preferably, PDMS in the step 2, curing agent, conductive powder body mass ratio be 10:1:(1.1-1.5).
Preferably, the mass ratio of mixture and PDMS microballoon is 1:(3-5 in the step 2), further preferably 1:
4。
Compared with prior art, beneficial effects of the present invention are as follows:
1, after carrying out the processing of conductive layer cladding to flexible PDMS microballoon, flexible macromolecule microsphere surface forms shell knot
Structure, wherein shell is the conductive layer that PDMS and conductive powder body collectively constitute so that conductive layer it is more stable in conjunction with PDMS microballoon,
Securely.
2, the shell thickness of flexible electronic skin is 20 nanometers -30 microns, and shell structurre also helps reduction conductive filler
Dosage；The superficial layer of electronic skin has sensitive mechanical response ability and stable electrical property.
3, preparation method of the present invention is easily operated and industrialization, and flexible electronic skin obtained has excellent comprehensive
Energy.
Detailed description of the invention
Fig. 1 is the schematic diagram of flexible electronic skin preparation method in the present invention.
Fig. 2 is the tensile stress strain curve figure for the flexible electronic skin that 1-4 of the embodiment of the present invention is obtained.
Fig. 3 is the surface for the flexible electronic skin that the embodiment of the present invention 3 obtains and scanning electron microscope (SEM) photo in section.
Fig. 4 is response curve of the obtained flexible electronic skin of the embodiment of the present invention 3 to pressure.
Fig. 5 is response curve of the obtained flexible electronic skin of the embodiment of the present invention 3 to shearing force.
Fig. 6 is the sensitivity curve for the flexible electronic skin that the embodiment of the present invention 3 obtains.
Specific embodiment
Technical solution of the present invention is described in detail below with reference to embodiment.
Embodiment 1-2
The preparation of PDMS microballoon: PDMS and curing agent, water are mixed according to the mass ratio of 10:1:50, and 6wt% is then added
Carboxyl chitosan to form lotion as emulsifier, using full and uniform be mixed with of centrifugal blender.Temperature by lotion at 80 DEG C
Degree is lower to solidify 2h, is then rinsed ten times with deionized water, centrifugation obtains PDMS microballoon.
PDMS, curing agent are mixed with graphene conductive powder according to mass ratio 10:1:(1.1-1.5), then with preparation
PDMS microballoon be uniformly mixed according to mass ratio 1:4 ratio centrifugal mixer, preparation forms the raw material ink of 3D printing；Utilize preparation
Raw material ink by three-dimensional printer printing-forming, be subsequently cured to obtain flexible electronic skin.
Wherein in embodiment 1 and embodiment 2 additive amount of graphene conductive powder be respectively skin gross mass 1.8%,
2.4%.
Participate in the schematic diagram that Fig. 1 is flexible electronic skin preparation method of the present invention.
Embodiment 3-4
The preparation of PDMS microballoon: PDMS and curing agent, water are mixed according to the mass ratio of 10:1:50, and 6wt% is then added
Carboxyl chitosan to form lotion as pre-emulsification agent, using full and uniform be mixed with of centrifugal blender.By lotion at 80 DEG C
At a temperature of solidify 2h, then with deionized water rinse ten times, centrifugation obtain PDMS microballoon.
PDMS, curing agent and carbon nanotube conducting powder according to mass ratio 10:1:(1.1-1.5) mix, then with system
Standby PDMS microballoon is uniformly mixed according to mass ratio 1:4 ratio centrifugal mixer, and preparation forms the raw material ink of 3D printing；Utilize system
Standby ink is subsequently cured to obtain flexible electronic skin by three-dimensional printer printing-forming.
Wherein the additive amount of 4 carbon nanotube conducting powder of embodiment 3 and embodiment be respectively skin gross mass 1.8%,
2.4%.
The flexible electronic skin that embodiment 1-4 is obtained is tested at room temperature, using the prepared electronics of DMA test
The stress-strain diagram of skin, obtained mechanical property result is referring to fig. 2.As can be seen from Figure 2: due to utilizing cladding process,
Realize the surface conductive layer cladding of PDMS microballoon so that PDMS microsphere surface forms conductive layer, due to conductive layer be PDMS with
Carbonaceous conductive material mixing composition, therefore conductive layer is firmly combined with PDMS microballoon, and can play the role of improving mechanical property.
By Fig. 2 it can be seen that 3 effect of embodiment is the most obvious, at the same the modulus of embodiment 3 it is similar to human skin modulus (0.13~
0.66MPa), illustrate that electronic skin produced by the present invention can keep height consistent with the deformation of human skin, can accurately respond
The deformation of skin.
Sem analysis is carried out to the flexible electronic skin of embodiment 3, SEM picture is referring to Fig. 3.As shown in Figure 3: table in structure
Layer forms shell structurre, and shell thickness is 20 nanometers -30 microns, and matrix is PDMS microballoon, and microballoon size is 6 microns -40 microns,
Wherein surface carbon nanotube layer is conductive layer.
The flexible electronic skin of embodiment 3 is placed in interdigital electrode, tests electronics skin using multi-axial forces/torque sensor
The mechanical response of skin, as a result referring to fig. 4.As can be seen from Figure 4: embodiment 3 realizes PDMS microballoon due to utilizing cladding process
Surface carbon nanotube cladding so that PDMS microsphere surface forms conductive layer, since conductive layer is that PDMS is mixed with carbon nanotube
Composition, therefore be firmly combined with PDMS microballoon.Under the effect of the pressure, mutual extrusion between microballoon and microballoon, leads to conduction
Access increases, and system resistance reduces, and realizes the response to pressure.Furthermore sensitivity can be effectively improved using micro-sphere structure, to power
Response is accurate and sensitive, and at low-pressure 0.12kPa, sensitivity has reached 2.08kPa-1。
The flexible electronic skin of embodiment 3 is subjected to shearing force response test, as a result referring to Fig. 5.As can be seen from Figure 5:
Flexible electronic skin can not only generate sensitive response to the effect of pressure, also have sensitive response to shearing force, for shearing
The variation of power is so that the reduction of system resistance, realizes the response to shearing force.Similar to the response of pressure, shearing force increases, microballoon
Mutual extrusion power increases between microballoon, and the distance between surface carbon nanotube is reduced, and conductive path is caused to increase, and corresponds to electricity
Sub- skin can generate corresponding resistive variation, to realize the response to shearing force.
The flexible electronic skin of embodiment 3 is subjected to sensitivity test, as a result referring to Fig. 6.As can be seen from Figure 6: flexible
Electronic skin can generate sensitive response to the effect of pressure, and pressure is smaller, and electronic skin shows higher sensitivity,
Due to utilizing cladding process, the surface carbon nanotube for realizing PDMS microballoon is coated, so that PDMS microsphere surface forms conductive layer,
Sensitive response can be generated to the effect of pressure.
It above are only part preferred embodiment of the invention, the present invention is not limited in the content of embodiment.For ability
For technical staff in domain, can there are various change and change in the conception range of technical solution of the present invention, made
What changes and change, within that scope of the present invention.
Claims (10)
1. a kind of multi signal responds flexible electronic skin, it is characterised in that: it is PDMS microballoon inside the flexible electronic skin,
PDMS microsphere surface covers conductive layer and forms shell structurre, and the partial size of the PDMS microballoon is 6-40 microns, the shell thickness
It is 20 nanometers -30 microns.
2. multi signal as described in claim 1 responds flexible electronic skin, it is characterised in that: the conductive layer is PDMS and lead
The mixture of electric powder, the additive amount of the conductive powder body are the 1.8%-2.4% of skin gross mass.
3. multi signal as claimed in claim 2 responds flexible electronic skin, it is characterised in that: the conductive powder body is received selected from carbon
One of mitron, graphene, graphene oxide, modified graphene oxide are a variety of.
4. the preparation method of multi signal response flexible electronic skin described in claim 1, which is characterized in that the method includes
Following steps:
Step 1, it prepares PDMS microballoon: PDMS, curing agent, water is mixed according to a certain percentage, emulsifier is then added, mixing is equal
Even formation lotion, solidification, deionized water are rinsed, and centrifugation obtains PDMS microballoon；
Step 2, it prepares the PDMS microballoon ink of conductive layer cladding: PDMS, curing agent, conductive powder body is mixed according to a certain percentage
It closes, mixture stirs evenly after mixing according to a certain percentage with the PDMS microballoon of aforementioned preparation, forms the raw material ink of 3D printing；
Step 3, by the raw material ink of preparation by 3D printer printing-forming, flexible electronic skin is made in solidification.
5. the preparation method of multi signal response flexible electronic skin as claimed in claim 4, it is characterised in that: the step 1
Middle PDMS, curing agent, water mass ratio be (8-12): 1:50.
6. the preparation method of multi signal response flexible electronic skin as claimed in claim 4, it is characterised in that: the step 1
The additional amount of middle emulsifier is 4-8wt%.
7. the preparation method of multi signal response flexible electronic skin as claimed in claim 4, it is characterised in that: the step 1
In emulsifier be carboxyl chitosan.
8. the preparation method of multi signal response flexible electronic skin as claimed in claim 4, it is characterised in that: the step 1
Middle solidification temperature is 70-90 DEG C.
9. the preparation method of multi signal response flexible electronic skin as claimed in claim 4, it is characterised in that: the step 2
Middle PDMS, curing agent, conductive powder body mass ratio be 10:1:(1.1-1.5).
10. the preparation method of multi signal response flexible electronic skin as claimed in claim 4, it is characterised in that: the step 2
The mass ratio of middle mixture and PDMS microballoon is 1:(3-5).
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| CN111928979A (en) * | 2020-07-22 | 2020-11-13 | 浙江理工大学 | Preparation method of high-sensitivity pressure sensor with hair follicle-like structure |
| CN114211744A (en) * | 2021-12-03 | 2022-03-22 | 宁波诺丁汉新材料研究院有限公司 | 3D printing self-filling multi-level porous sensor and preparation method thereof |
| CN115537028A (en) * | 2022-09-29 | 2022-12-30 | 四川大学 | Preparation method of conductive silicone rubber composite material with interface enhanced isolation structure |
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| CN111928979A (en) * | 2020-07-22 | 2020-11-13 | 浙江理工大学 | Preparation method of high-sensitivity pressure sensor with hair follicle-like structure |
| CN111928979B (en) * | 2020-07-22 | 2022-02-15 | 浙江理工大学 | Preparation method of high-sensitivity pressure sensor with hair follicle-like structure |
| CN114211744A (en) * | 2021-12-03 | 2022-03-22 | 宁波诺丁汉新材料研究院有限公司 | 3D printing self-filling multi-level porous sensor and preparation method thereof |
| CN115537028A (en) * | 2022-09-29 | 2022-12-30 | 四川大学 | Preparation method of conductive silicone rubber composite material with interface enhanced isolation structure |
| CN115537028B (en) * | 2022-09-29 | 2023-06-23 | 四川大学 | Preparation method of conductive silicon rubber composite material with interface enhanced isolation structure |
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